Preservation of oils, fats, fatty oils, fatty esters, fatty acids, fatty acid salts, and related compounds



' Patented 1 935 1mm. STATES PATENT OFFICE rassaava'rrou or ram as'raas, scm ssn'rs, AND

notation of Delaware oms. rs'rs, ram oms. FATTY ACIDS. FATTY neuron commas William, S. Calcott and William A. Douglass,

Pennsgrove, N. J., and Herbert W. Walker, Wiln, DeL, asaignors'to E. I. Nemours & Company, Wiimingto du Pont de n,Del.,acor- No Drawing. Application December 18, 1929,

Serial No. 415,016

-2'iClaims.

to retard deterioration and .development of rancidification. More particularly it pertainsto the addition of organic compounds to such substances in order to accomplish these results. Specifically, the incorporation. of diaryl. or diarallryl compounds, such as oxy-diaryl amines into-the material ,to be preserved is contemplated.

Butter, lard, cocoanut oil and other animal and vegetable fats and fatty oils, together with soap, the sodium or potassium salts of the 'fattyacids contained in these fats and fatty oils, tend to 'develop an objectionable rancid odor and taste on exposure to air under ordinary conditions. This deterioration is due to the oxidation of the fatty acid part'of the fat or soap molecule by atmospheric oxygen. The oxide derivatives which are first formed become decomposed or altered and produce substances having a rancid odor and taste.

Some work has been done in the fat preservation field as shown by U. S. P. 1,542,438 to Divine, wherein aniline, alpha naphthylamine, para phenylene-diamine, diphenylamine and hexa-' methyle'netetramine are added to soap. InU. S. P. 1,575,529'to Bollman soya bean lecithin is added to edible oils. Other improvements in the keeping quality of auto-oxidizable substances are claimed in U. S. P.-1,672,657'to Powell according to which the condensation product of an aromatic amine and an aliphatic aldehyde is added to the material to be preserved. The foreign patent art also discloses work along this line as evidenced by B. P. 181,865 to Moureu and Du l'raisse who employ the phenols such as pyrogallol, guaiacol, and hydroquinone as stabilizers for auto-oxidizable substances. In B. P. 208,189 a Lever Bros.

the phenols of the types hydroquinone, guaiacol and resorcinol are used to prevent deterioration of whale oil. Rechburg, Braum; and Oetermann in n. R. P. 254,303 disclose sulfur and py saliolfor the preservation of oils and-fats. 'Boehringer in D. R. P. 308.408 discloses alkali lactates as illitable stabilizers formargarine, butter and lard.

Many of the compounds heretofore employed,.

however, have been. open to the objection that they either discolorthe product to-be preserved or 'form compounds that have this objectionable property. Certain-compounds. of the prior art impart to theproduct in which they are incorporated a distinctiveodor. Other proposed preventives are actually ineffectual or are effective only for,a. short time. i I 1 of the odors given oil) for along period, to main tain the original chemical and physical states for extended periods, to prevent reaction of these substances or their constituent parts with the at-' mosphere or its constituent parts. such as oxythe like. A further Object of gen. to prevent oxygen 'absorptionby the materials to be preserved and generally overcome the objectionable features of the priorart. Other objects will appear hereinafter. These objects are accomplished by the invention herein disclosed which is related to the invention of application No. 391,706, filed September 10, 1929, by the same inventors in that fit involves further work in the same field. Inthat applicationthe preservation of oils, fats, etc. by the'addition thereto of diaryl compounds is disclosed and in. the examples set forth the aryl groups are directly connected. It-has now been found that preservation may also be accomplished by compoundscontaining a plurality of aryl groups connected through or to an intermediary, for examplqan amino radical. In compounds of this clam, those having a hydroxy, alkoxy or amino radical attached to an aryl group are particularly effective.

According u: this invention members of the oxy-diaryl-amine class of organic compounds are incorporated into the substances to be preserved. When so incorporated they act as antioxidants to-prevent combination with or absorption of oxygen thereby delayingor preventing,

deterioration and ultimate rancidi ty. The general formula of the compounds used is.

xo-n mre-n -r .where R and R. are aryl 'or aralbl which are alike or difierent, x is hydrogen or alkyl, and

r Example 1 y when 0.1% .p-hydroxy diphenyl'amine was introduced into commercial-lard and oxidation .measurements made at 60 C. in an omen atmosphere of 80% relative humidity ontreated I and untreated samples it was found that the sample containing p-hydroxy diphenylarnine required hours to absorb 2% by. weight of oxygen, whereas the untreated control sample absorbed this amount of oxygen in 9 hours. Oxi

dation is retarded and likewise the deterioration and development of rancidlty accompanying normal oxidation.

' Example I! White olive castile' soa'p containing 0.1%

p-ethoxy phenyl-a-naphthylamine'was protecte naphthylamine more than 160 hours were required tor 2.5% oxygen to be absorbed. The treated sample possessed a sweet, mun-rancid odor at' the end of this time while the untreated control was strongly rancid.

1 Example In "11' 0.2% p-hydmxy diphenylamine be income rated in cocoanut'oil and the vegetable oil be exposed to the action of atmospheric oxygen at 60 C. in such a way as to measure the rate and extent of oxygen absorption manometrically it' is round that the treated soap absorbs oxygen at a much slower rate than an untreated control oil sample. An inhibition of oxidation is secured by the use of p-hydroxy diphenylamine resulting in an improvement in the aging qualities of the oil I whichotherwise would have become deteriorated and rancid.

It will be understood that the concentrations of antioxidant agents may vary to secure protection against deterioration to a less and greater degree depending on the nature of the rat, fatty oil or soap in question, the nature of the antioxidant, and the actual concentration of agent efiectiveness. It will,

when the aryl groups have substituents other,

used. Ordinarily the amount of the preservative used ranges from 0.001 to 1.% but this invention contemplates greater amounts 1! there be a particular need therefor, although so far it" has not been found necessary to use more than the maximum amount stated above. listed are not harmful so far as applicants are aware, but it is probably advisable to limit their use in edible materials to small quantities. Ac-' cordingly the particular conditions 01 each case will determine the amount needed.

In the examples of antioxidants listed further on in this specification certain aryl groups in this class of compounds are disclosed, for instance, phenyl, naphthyl and biphenyl. It is to be understood that these are given as illustrative and not as limiting. Use ofv any other aryl groups such as tolyl, and xylyl may be made with of course, be obvious that than oxy groups that the same must be oi such nature as not to neutralize the oxy radical or nullify the inhibitive effect of the main nucleus, and furthermore must be compatible with the object in view.

As examples of the class oi compounds de- The preservatives scrlbecbabove which may be used eil ectivelythe following are givenz-ep-bydrox y diphenylamine, f

G Q p-ethoxy pheuyl-a-naphthylamine, wa

p-hydroxy plienyl-beta-naphthylamine, l5

pp'diethoxy dlphenylsmine, o omoOrmG-ooun pp'-dlhydroxy dlphenylamiu .HbO-NK-O-OH 25 -p-butyloxy diplienylamine, Q Q

I 'pp'-dibutyloxy diplienylsmlne, @moOnn-O-oom pheuyl-d-hydroxy-a-naplithylamine, 35 I -4o" p-bydroxy:phenyl-b-hydroxy-a-naphthylamine,

y o p-hydroxy phenyl-p-toluldlne, .no-O-mrQ-cm 50 2: 2"dibydroxydi-a-uaphthylamina, I

p-hydroxy diplieuyl-a-naphthylamlne, GO

. p-hydroxy phenyl diphenylamlne, 05 I I I 3 3'-dihydroxy' 2 2'-dlnapbthylamiue,

OH HO tarded, delayed or prevented in such a way that they remain sweet and apparently unchanged for long periods of time.

Of the oxy-diaryl-amines the aikoxy-diphenyl amines are preferred. Bpeciaily good results have been obtained with p:p'-diethoxy-diphenylunder ordinary conditions.

As many apparentlywidely different embodiments of this invention may be made without departing from 'the spirit and scope thereof, it is to be understood that we do not limit ourselves I to the specific embodiments thereof except as defined in the'appended claims.

We claim: 1. A member of the group fats, fatty oils. fatty esters, fatty acids and fatty acid salts together,

.pound capable of rancidiiication and as an oxiwith 0.001 to 0.2% para: para' diethon-diphenylamine as an oxidation inhibitor and rancidiiication preventative. Y

2. .A composition of matter containing a member of the group oils, fats, fatty oils, fatty esters, fatty acids, fatty acid salts, and the like tending to develop rancidity togetherwith an oxidation inhibitor and rancidiiication retarder comprising.

a compound having a plurality of aryl groups joined to an amino nucleus and at least one of.

said aryl groups being substituted. 3. A composition of matter containing a member of the group fats, fatty oils, fatty esters, fatty acids, fatty acid salts and the like together with an oxidation inhibitor and rancidiiication retarder comprising a compound havinga plurality of aryl groups Joined to an amino nucleus and at least one of said aryl groups having an on substituent. d

4. A composition of matter containing a memberof the group fats, fatty-oils, fatty esters, fatty tarder comprising acompound having a plurality of aryl groups joined to an amino nucleus at least one of said aryl groups being a phenyl'group and at least one of said aryl groups having a substituent other than a nitro or sulfonic group.

6. A compomtion of matter containing a mem-' ber of the group fats, fatty oils, fatty esters, fatty acids, fatty acid salts and the like together with an oxidation inhibitor and rancidiiication retarder comprising a compound having a plurality of aryl groups joined to an amino nucleus at least,

one ofsaid aryl groups being a phenyl group,'and at least one'of said aryl groups having an oxy substituent.

'I. A composition of matter containing amember of the group fats, fatty oils, fatty esters, fatty acids. fatty acid salts and the like together with an oxidation inhibitor and rancidiflcation retarder comprising a compound having a plm'aiity of aryl groups ioinedto anaminonucleusat least at least one of said aryl groups having substituent. Y a

8. A composition of matter'containinga mem- .ber of the'group fats, fatty oils, fatty esters, fatty acids, fatty, acid salts and thelike together with an. oxidation inhibitor and rancidiiication retarder comprising a compound having a plurality of aryl groups 'Joined to an amino nucleus at leasttwo of said aryl groups-being phenyl groups and at least one of said-aryl groups being ethomr sub stituted.

9. A composition of matter containing a member of the group fats, fatty oils, fatty esters, fatty acids, and fatty acid salts and as an oxidation one of said aryl nouns being a phenyl group, and an ethoxy' inhibitor and rancidincation preventative .a compound of the class X ORNHR'-- where 'R and R are aryl or aralkyl groups which maybe alike or different, x is hydrogen or alkyl and Y is hydrogen, hydroxy or aikoxy.

10. A composition of matter containing a comdation inhibitor and rancidiilcation preventative a compound of the alkoxy-diarylamine class. 11. A compomtion of matter containing a member of the group fats, fatty oils, fatty esters, fatty acids, and fatty acid salts and as an oxidation inhibitorandrancidiiication preventative a com- P und of the alkoxy-diaryiami'n'e class.

12. Acomposition of matter containing a member of the group fats, fatty oils, fatty esters, fatty.

acids, and fatty acid'salts and as an oxidation inhibitor and rancidification preventative a compound of the ethoxydiphenylamine class.

13. Animal fat together with an alkoxy-diarylamine as an inhibitor of rancidiiication.

.14. Lard together witiran alkoxy-diaryl-amine as an inhibitor of ranoidiilcation.

- 15. Vegetable fat together with an alkoxy di aryl-amine as an inhibitor of rancidiilcation.

'16. Cocoa-nut oil together with an alkoxy-diaryl-amine as an inhibitor of rancidification. a 17. Soap together with an alkoxy-diaryl-amine as an inhibitor of rancidification.

18. The composition of claim 1'1 in which the aikoxy-diaryl-amine is an ethoxy-diaryl-amine.

- 19. line composition of claim 17 in which the alkon-diaryl-amine .is an ethoxy-diphenylamine.

. so. a composition of matter probably comprising-a member of'the group consisting of fats,

fatty oils, fatty esteraffatty acids and fatty acid salts and an alkon diaryl-amine which is sub-' stantiaily identical with the product resulting from incorporating an aikoxy diaryl-amine in a member of the aforesaid group. 1 I

21. A composition of matter composed of a fatty oil subject to the development of rancidity together with a rancidiiication retarder of the class consisting of p-hydroxy diphenylamine; pp-

dihydro'w diphenylamine, and p-butoxy diphenyiamine.

221A composition of matter composed of a fatty oil subject to the development of rancidity gether with an oxy-di-aryl-amine from the group consisting of" hydroxyand alkoxy-di-arylamines as a preservative.

26. A composition of matter composed of a fatty I m1 subject to the development o! rancidity tow gether with an oxy-di-phenylamine from the Patent No. 1,987,321.

40, strike out andthat thesaid Letters Patent should be read with this correction same may conform to the record of the case in the Patent Office.

of March, A. D. 19353 3 Signed and sealed-this 19th day WILLIAMS. oALoo'r'r ET AL.-

It is hereby certified that error appears in-the printed specific numbered patent 'requmng correctmn as follows: Page 2, second column,

the formula and Insert insteadgroup consisting 0! hydroxyand alkoxy-diphenyl-amines as a preservative.

2'7. A composition of matter composed of a fatty oil subject to the development of rancidity together with an oxy-phenyl-naphthyl-amine from the group consisting of hydroxyand alkoxy-phenyl-naphthyl-amines as a preservative.

S. CALCOTT. WILLIAM A. DOUGLASS. HERBERT W. WALKER.

cate of Correction January 8,1935."

ation of the above hnes 35 to therein that the LESLIE "FRAZER, Acting Commissioner of Patents Patent No, 1,987,321.

Certificate of Correction WILLIAMS. CALCOTT ET AL.-

( January 8,1935.

It ie hereby certifie that error appears in-the printed Specification of'the ebove numbered patent'requmng corgection as follows: Page 2, second column, lines 35 to 40, stnke out the formu'la. and mser't instead- 4 t T andthat thesaid Letters Patent should he read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed-and sealed this 19th day of March, A. D. 1935, l

4 sm' LESLIE FRAZER,

Acting Commissioner of PM, 

